Kiyoshi Tomioka · Takayuki Shioiri Hironao Sajiki E ditors New Horizons of Process Chemistry Scalable Reactions and Technologies New Horizons of Process Chemistry Kiyoshi Tomioka Takayuki Shioiri (cid:129) Hironao Sajiki Editors New Horizons of Process Chemistry Scalable Reactions and Technologies 123 Editors Kiyoshi Tomioka Hironao Sajiki DoshishaWomen’s Collegeof LiberalArts GifuPharmaceutical University Kyotanabe Gifu Japan Japan Takayuki Shioiri Meijo University Nagoya Japan ISBN978-981-10-3420-6 ISBN978-981-10-3421-3 (eBook) DOI 10.1007/978-981-10-3421-3 LibraryofCongressControlNumber:2016963739 ©SpringerNatureSingaporePteLtd.2017 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. 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Theregisteredcompanyaddressis:152BeachRoad,#21-01/04GatewayEast,Singapore189721,Singapore Preface Process chemistry will be one of the most important sciences in the twenty-first century.Itpassesthebatoninarelayracefromdiscoveryofusefulnewmaterialsto their industrial production. Economic and environmentally benign procedures are essential. Because the stagnation of process chemistry is estimated to cause industrial depression and excessive loss, chemists focus on process chemistry consistently to provide a stimulus by the development of novel and efficient new methods, reactions, and technologies applicable to scalable production. In December 2015, the International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015) was held in Hawaii, and the symposium “NewHorizonofProcessChemistrybyScalableReactionsandTechnologies”was convened as one of the technical programs, supported by the Japanese Society for Process Chemistry. A series of interesting lectures by 35 speakers was delivered, and 33 topics were presented at the poster session. Topics of these lectures and presentations included new catalysts, reactions, and methods for the synthesis of functional materials including pharmaceuticals, agrochemicals, chemical raw materials, and other materials oriented toward process chemistry, with green and sustainable chemistry as one of the major topics. Furthermore, various isolation methods including crystallization, development of reactors and equipment, direct observational methods of the progress in reactions, and process design to increase scale were also important topics. Thisbookisaselectionoftheabove-mentionedpresentations;however,itisnot a proceedings of the symposium but rather a collection of mini-reviews based on the presentations. Readers will be able to enjoy reading about the latest develop- ments in the field of process chemistry, new methodology intended for process chemistry, and medicinal chemistry. Wehopeprocesschemistrywillbemoreproductiveandwillflourishinthenear future. Kyotanabe, Japan Kiyoshi Tomioka Nagoya, Japan Takayuki Shioiri Gifu, Japan Hironao Sajiki v Contents Recent Advances in Rare Earth Metal Asymmetric Catalysis Toward Practical Synthesis of Therapeutics.. .... .... .... ..... .... 1 Naoya Kumagai and Masakatsu Shibasaki Metal Catalyzed Synthetic Reactions via Aerobic Oxidation as a Key Step . .... .... .... ..... .... .... .... .... .... ..... .... 11 Mitsuru Shindo and Kenji Matsumoto Heterogeneous Platinum Metal Catalyzed Deuterium Generation and Labeling Methods Using Hydrogen Gas and Deuterium Oxide as Key Reagents.. .... .... .... .... ..... .... 29 Hironao Sajiki Pd on Spherical Carbon (Pd/SC)-Catalyzed Chemoselective Hydrogenation. .... .... .... ..... .... .... .... .... .... ..... .... 41 Hiroyoshi Esaki Environment-Friendly Iron-Catalyzed Reactions .. .... .... ..... .... 51 Yoshinari Sawama Tetranuclear Zinc Cluster-Catalyzed Transesterification.... ..... .... 65 Takashi Ohshima Vinyl Ruthenium Carbenes: Valuable Intermediates in Catalysis.. .... 89 Damián Padín, Jesús A. Varela and Carlos Saá Radical-Based Late Stage C–H Functionalization of Heteroaromatics in Drug Discovery .. .... .... .... .... ..... .... 103 Yuta Fujiwara and Phil S. Baran Magnetic Nanoparticle-Supported Iodoarene Oxidative Catalysts and Its Application to Phenol Oxidation. .... .... ..... .... 121 Hisanori Nambu, Ikumi Shimokawa, Tomoya Fujiwara and Takayuki Yakura vii viii Contents Recent Development of Diphenyl Phosphorazidate (DPPA) as a Synthetic Reagent .. .... ..... .... .... .... .... .... ..... .... 131 Takayuki Shioiri Methylenation Reaction of Carbonyl Compounds Using Julia-Kocienski Reagents .... ..... .... .... .... .... .... ..... .... 147 Kaori Ando Development of Shelf-Stable Reagents for Electrophilic Trifluoromethylthiolation Reaction . .... .... .... .... .... ..... .... 163 Zhongyan Huang and Norio Shibata Practical and Environmentally Friendly Transformation of Tetrahydrofuran-2-Methanols to c-Lactones via Oxidative Cleavage . .... .... .... .... ..... .... .... .... .... .... ..... .... 179 Tomoya Fujiwara, Yuto Horiuchi, Akihiro Yamada, Hisanori Nambu and Takayuki Yakura Five Step Asymmetric Total Synthesis of b-Lycorane Employing Chiral Diether Ligand-Controlled Conjugate Addition-Michael Reaction Cascade .. .... .... ..... .... .... .... .... .... ..... .... 191 Kiyoshi Tomioka Concise Synthesis of Peptide Analogs Using a Fluorous-Fmoc Protection Strategy. .... .... ..... .... .... .... .... .... ..... .... 201 Masato Matsugi A Challenging Synthesis of the Highly Functionalized Echinocandin ASP9726: A Successor of Micafungin—How Can We Achieve the Large-Scale Synthesis? . .... .... .... .... ..... .... 217 Shinya Yoshida, Joji Hayashida, Yasuhiro Morinaga, Shoji Mizobata, Akihiro Okada, Kazumi Kawai, Shinjirou Tanoue, Tomohide Nakata, Minoru Kitayama, Atsushi Ohigashi, Mitsutaka Matsuura, Takumi Takahashi, Shigeru Ieda and Minoru Okada The Role of Silyl Protecting Group for the Synthesis of Procyanidins and Their Derivatives .. .... .... .... .... ..... .... 229 Noriyuki Nakajima and Akiko Saito Chemical Modification of the 3′-Dangling End of Small Interfering RNAs Such as siRNAs and miRNAs: The Development of miRNA Replacement Therapy.... .... ..... .... 237 Yukio Kitade, Takashi Mori and Yukihiro Akao Contents ix AntiviralAgentsTowardsChikungunyaVirus:Structures,Syntheses, and Isolation from Natural Sources. .... .... .... .... .... ..... .... 251 Jih Ru Hwu, Tapan K. Pradhan, Shwu-Chen Tsay, Mohit Kapoor, Sergey O. Bachurin, Oleg A. Raevsky and Johan Neyts Analytical Standards Purity Determination Using Quantitative Nuclear Magnetic Resonance. ..... .... .... .... .... .... ..... .... 275 Toru Miura, Naoki Sugimoto, Takako Suematsu, Kevin K. Millis, Katsuo Asakura and Yuko Yamada Recent Advances in Rare Earth Metal Asymmetric Catalysis Toward Practical Synthesis of Therapeutics Naoya Kumagai and Masakatsu Shibasaki Abstract Two case studies regarding the development of rare earth metal-based asymmetric catalysts are summarized, with particular focus on the process of refiningcatalystsamenabletoindustrialapplications.Amide-basedchiralligandsin combination with lanthanum or neodymium cations furnished robust catalytic systems for asymmetric amination or nitroaldol reactions, respectively. Although rare earth metal catalysis is generally characterized by a peculiar coordination chemistry and Lewis acidic catalytic functions, its wide availability and moderate tolerancetomoisturearealsoimportantfeaturestobenoted,makingtheapplication of rare earth metal catalysis beneficial for industrial large-scale synthesis. (cid:1) (cid:1) (cid:1) (cid:1) Keywords Amination Asymmetriccatalysis Flowreaction Nitroaldol Rare earth metals 1 Introduction Homochirality has become an indispensable feature for the manufacture of active pharmaceutical ingredients (APIs), attracting increasing attention to enantioselec- tive catalysis in medicinal and process chemistry as an efficient method for pro- ducing chiral building blocks of interest. Efficiency in lab-scale synthesis and feasibility in large-scale operations, however, are often difficult to achieve in par- allel; the majority of newly developed methods in enantioselective catalysis are rarely applied to industrial applications. Particularly for chiral hard Lewis acid catalysts,therequirementforrigorousdryingofthesubstratesandreaction vessels to achieve high fidelity in the reaction severely hampers industrial application. N.Kumagai(&)(cid:1)M.Shibasaki(&) InstituteofMicrobialChemistry(BIKAKEN),3-14-23Kamiosaki, Shinagawa-kuTokyo141-0021,Japan e-mail:[email protected] M.Shibasaki e-mail:[email protected] ©SpringerNatureSingaporePteLtd.2017 1 K.Tomiokaetal.(eds.),NewHorizonsofProcessChemistry, DOI10.1007/978-981-10-3421-3_1 2 N.KumagaiandM.Shibasaki Herein we document chiral rare earth metal catalysts that are promising for prospective applicationin large-scaleindustrial operations. Despitethe term ‘rare’, not all ‘rare’ earth metal are expensive and available in only small quantities [1]; indeed, the natural abundance of lanthanum, one of the most representative rare earthmetals,intheearth’scrustisclosetothatofzincorboron.Therelativelylow toxicity concerns of rare earth metals are also favorable for application to the manufacture of APIs. This chapter summarizes two rare earth metal-based asym- metric catalysts featuring lanthanum and neodymium as key components respon- sible for catalytic functions. 2 La-based Catalysis: Catalytic Asymmetric Amination Nitrogen is a key element embedded in carbon-based skeletons in a myriad of natural products and therapeutics, thereby the development of synthetic method- ologies to incorporate nitrogen functionalities have been a sustained topic in organic synthesis. Electrophilic amination utilizing azodicarboxylates as elec- trophiles is commonly exploited to install nitrogen functionality in certain nucle- ophiles, including latent enolates [2]. Despite its early discovery [3–5], no enantioselective variants were reported until Evans et al. disclosed catalytic asymmetric a-amination of N-acyloxazolidines and enolsilanes promoted by Mg and Cu complexes in the late 90s [6, 7]. Since this demonstration of enantiose- lective introduction of nitrogen functionality, the flurry of reports on catalytic asymmetricaminationappearedbased onbothorganocatalystsandmetalcatalysts, and has been compiled in various review articles [8–12]. In this context, we were particularly intrigued by the fact that simple succinimide-typesubstrate1eludedtheintroductionofanitrogenfunctionalityina catalyticandenantioselectivemanner(Scheme 1).Aminationproduct2isaknown key intermediate of ranirestat(AS-3201)[13, 14],whichis under clinical trials led by Dainippon-Sumitomo Pharma for the treatment of diabetic neuropathy. Previously identified organocatalysts and metal-based catalysts in the literature Scheme1 Catalytic asymmetric amination of succinimide derivative 1 for the enantioselective synthesisofranirestat,acandidatedrugfordiabeticneuropathy